EP0044214A2 - Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same - Google Patents

Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same Download PDF

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Publication number
EP0044214A2
EP0044214A2 EP81303181A EP81303181A EP0044214A2 EP 0044214 A2 EP0044214 A2 EP 0044214A2 EP 81303181 A EP81303181 A EP 81303181A EP 81303181 A EP81303181 A EP 81303181A EP 0044214 A2 EP0044214 A2 EP 0044214A2
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Prior art keywords
alkyl
alkoxy
ethyl
cyano
alkylthio
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EP81303181A
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German (de)
French (fr)
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EP0044214B1 (en
EP0044214A3 (en
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Leonard Edward Hodakowski
Hafez Mohammed Ayad
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4087—Esters with arylalkanols
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1653—Esters of thiophosphoric acids with arylalkanols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/177—Esters of thiophosphoric acids with cycloaliphatic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2429—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of arylalkanols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings

Definitions

  • This invention relates to novel phosphorous esters of cyanohydrins and methods of preparing same.
  • This invention is also directed to a pesticidal composition comprising an acceptable carrier and a pesticidally effective amount of a compound of this invention, as well as to a method of controlling pests which comprises subjecting the pests to a pesticidally effective amount of a compound of this invention.
  • the patentee reacts acetone cyanohydrin with A to yield Diethyl 1-cyano-1-methyl ethyl phosphate as shown below.
  • one of the 0-ethyl groups is replaced by an S-n-propyl group which unexpectedly increases the broad cpectrum pesticidal activity over the compounds disclosed in U.S. Patent 2,965,533.
  • novel compounds can be represented by the following generic formula: wherein X is 0 or S;
  • compositions falling within the above generic formula exhibit biological activity as pesticides to a greater or lesser extent. Some exhibit very powerful activity in extremely small dosages while others require larger dosages to be effective.
  • the phosphorous esters of this invention can be conveniently prepared utilizing appropriate aldehydes and ketones as starting materials. These are converted to their corresponding cyanohydrins (1-4) and then reacted with a phosphorylating group as shown below. wherein the values of X, R, R 1 , R 2 and R 3 are as indicated previously.
  • the aldehyde or ketone (C) can be converted to cyanohydrin (D) using one of the four methods listed or variations thereof.
  • the choice of which method is used is dependent upon the substituents R and R 1 .
  • Conversion of D ⁇ E occurs by reacting one equivalent of cyanohydrin with an appropriate chloro phosphorous compound in the presence of at least one equivalent of an acid acceptor, preferably in an inert solvent.
  • the acid acceptor utilized in this reaction scheme (D ⁇ E) can be either an organic or inorganic base.
  • organic bases that are useful acid acceptors are tertiary amines, such as triethylamine, 4-N,N-dimethylamino pyridine, pyridine, trimethyl amine, collidine or 1,4-diazobicyclo [2.2.2] octane; bases such as sodium carbonate and potassium carbonate are illustrative of inorganic bases that are useful acid acceptors.
  • any organic solvent that is inert to the reactants or reaction conditions may be employed in the reaction scheme shown above.
  • organic solvents which are generally suitable for use in conducting these reactions are saturated, unsaturated and aromatic hydrocarbons, e.g. hexane, cyclohexane, octane, cyclohexene, dodecane, naptha, decalin, kerosene, cyclopentane, benzene, toluene, xylene, napthlene or the like; others such as dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethyoxybenzen, the dialkyl ethers of ethylene glycol, or propylene glycol or chlorinated aliphatic hydrocarbons, as for example, chloroform, dichloromethane 1,1-dichloroethane, carbon tetrachloride, and the like, are also acceptable.
  • the reaction sequence D ⁇ E may also be conducted in a solvent which functions as an acid acceptor.
  • a solvent which functions as an acid acceptor.
  • multifunctional colvcnts are N,N-dimethylaniline, pyridine, collodine or any like aromatic or heterocyclic tertiary amine compound.
  • the reaction sequence (C ⁇ D ⁇ E) can be conducted over a broad temperature and pressure range to yield the desired products, preferably, these reactions are conducted at a temperature of -40°C to about 60°C and at atmospheric or autogeneous pressure.
  • the phosphorous halides utilized as reactants in the scheme D ⁇ E generally are known materials which can be obtained from commercial sources or prepared in accordance with conventional methods known to those skilled in the art.
  • pesticidally active compounds are illustrative of compounds within the purview of the above generic formula and which can be conveniently prepared by the process of this invention simply by selecting appropriate reactants for use in the procedures described below.
  • a 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel and drying tube. The glassware was dried and to this was charged 21.2 grams (0.2 mole) benzaldehyde and 19.5 grams (0.3 mole) potassium cyanide dissolved in 70 ml of water. The reaction flask was cooled to 10-15°C using a water/ice bath. To this was added 70 ml of 40% sulfuric acid over a 60 minute period. After the addition was complete, the reaction was allowed to warm to room temperature and stir for an additional two hours.
  • reaction mixture was extracted with carbon tetrachloride (3x75 ml), washed the combined carbon tetrachloride layers with water (2x50 ml), dried the carbon tetrachloride layer with anhydrous magnesium sulfate, filtered and concentrated to yield benzaldehyde cyanohydrin.
  • a 100 ml round bottom flask fitted with thermometer, water condenser with drying tube and magnetic stirring bar has charged into it 2.8g (.033 mole) acetone cyanohydrin, 3 drops triethylamine and 50 ml carbon tetrachloride.
  • the reaction mixture is cooled to 0°C using a water/ice bath.
  • 5.9g (.03 mole) of pentafluoro benzaldehyde is added to the reaction mixture at a rate which allows the temperature to be maintained between 5-15°C. After all the aldehyde is added the reaction is brought up to room temperature and stirred overnight.
  • reaction is cooled to 15°C (water/ice bath) and 2.4g (.03 mole) pyridine is added followed by the addition of 6.0g (.03 mole) 0-ethyl-S-n-propyl phosphoro chloridate while maintaining a temperature of less than 20°C. After the chloride is added the reaction is brought to room temperature and stirred overnight.
  • a 100 ml round bottom flask fitted with thermometer, water condenser with drying tube and magnetic stirring bar has charged into it 6.0g (.0405 mole).
  • the material was stirred overnight at room temperature and then transferred to a 250 ml flask at which time 60 ml of 3N hydrochloric acid was added end the mixture stirred for three hours at room temperature.
  • the material was taken up in ethyl ether, dried over anhydrous magnesium sulfate, filtered and concentrated in vecunm.
  • Examples 4-45 illustrate other compounds of the present invention which were prepared by methods detailed in this invention.
  • Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent.
  • the resulting solution was mixed into 150 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form.
  • the thus-prepared stock suspension contained 0.5 percent by weight of compound.
  • concentrations in parts per million by weight employed in the tests described below were obtained by appropriate dilutions of the stock suspension with water.
  • test compounds were formulated by diluting the stock suspension with water to give c suspension containing 500 parts of test compound per million parts of final formulation.
  • the potted plants (one pot per comperund Leated) infested with 100-150 aphide, were placed on a revolving turntable and aprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 acconds, was sufficient to wet the plants to run-off.
  • 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting.
  • test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
  • Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and aprayed with 100-110 milliliters of test compound formulation by use of a DeVilbias spray gun set ct 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off.
  • 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on plants. When dry, the paired leaves were separated and each one was placed in a 9 centimeter Petri dish lined with moistened filter paper.
  • test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
  • Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off.
  • 100-110 milliliters of a water-acetone-emulsifier solution containing no teet compound were also aprayed on plants. When dry, the paired leaves were separated nnd each was placed in a 9 cantimetor Petri dich lined with moistened filter paper.
  • test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final formulation, by weight.
  • Ten milliliters of the test formulation were added to a soufflé cup containing a one-inch square of an absorbent cotton pad. This bait cup was introduced and centered on the blotting paper under the food strainer prior to admitting the anesthetized flies.
  • the caged flies were allowed to feed on the bait for twenty four hours, at a temperature of 80 ⁇ 5°F, and the relative humidity of 50 ⁇ 5 percent. Flies which showed no sign of movement on prodding were considered dead.
  • Test organisms Adults and nymphal stages of the two-spotted mite (Tetranychus urticae Koch), reared on Tendergreen bean plants at 80 ⁇ 5°F and 50 ⁇ 5 percent relative humidity were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. 150-200 Mites, a sufficient number for testing, transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
  • the potted plants (one pot per compound) were placed on a revolving turntable and'sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 seconds, was sufficient to wet the plants to nun-off.
  • 100-110 milliliters of water solution containing acetone and emulsifier in the same concentration as the test compound formulation, but containing no test compound were also sprayed on infested plants.
  • the sprayed plants were held at 80 + 5°F and 50 ⁇ 5 percent relative humidity for six days, after which a mortality count of motile forms was made. Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living.
  • Infective migratory larvae of the root-knot nematode Meloidogyne incognita ver. acrita, reared in the greenhouse on roots of tomato (Florida M-1) and cucumber (National pickling), constituted the test organism.
  • This particular nematode incites distinct galls or knots on the roots of certain plants.
  • Infected roots, containing egg masses were removed from the stock culture and cleaned of soil by shaking and washing with tap water. Roots were finely chopped, then vigorously shaken in a 0.5 percent NaOCl solution for 4 minutes.
  • To separate the nematode eggs from root tissue the mixture was poured through a 32-mesh sieve nestled in a 500-mesh sieve followed by a gentle stream of water to remove any trace of NaOl.
  • the trapped eggs were rinsed with water into a 50-mt beaker. Samples of the egg suspension were counted with the aid of a stereoscopic microscope. 4000 to 6000 eggs were added to a series of pint mason jars, each containing 180 cc. of soil. The jars were capped and mixed thoroughly to insure uniform infestation of the soil. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 3.3 mg of test compound per 10 ml of final formulation which when added to the jar of coil was approximately equal to a rate of 28 kilogram of test compound per acre. Following addition of formulation, the jars were tightly capped, and the contents were thoroughly mixed on a ball mill for five minutes.
  • the jars remained capped for 48 hours after which the contents were transferred to three inch diameter pots.
  • the coil was then planted with cucumber seeds, and since cucumber is susceptible to root-knot nematode attack, it served as an indicator crop.
  • the pots were then placed in a greenhouse. After 4-6 weeks, the cucumber plants were removed from the pots, the roots were washed free of adhering soil, and directly compared with the roots of similar plants grown in infested but untreated soil. The averaged degree of gall formation on the roots of the cucumber plants was the basis for ascertaining nematode control.
  • pest species employed in the above tests arc merely representative of a wide variety of plant pests that can be controlled by the use of the compounds of this invention.
  • the compounds contemplated in this invention may be applied as mite ovicides and miticides according to methods known to those skilled in the art.
  • the compounds of the instant invention are useful as fumigants for grain insects, have soil insecticidal activity against the corn root worm, and also possess systemic activity.
  • Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
  • Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents.
  • Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying and dispersing agents.
  • dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re- emulsify the toxicant after it is applied to the plant and wash it off the plant.
  • Nonionic, anionic. amphoteric or cationic dispersing and emulsifying agents may be employed; for example, the condensation products of alkylene oxidec with phenol and organic acids,. alkyl aryl sulfonates, complex, other alcohols, quaternary ammonium compounds, and the like.
  • the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like.
  • an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like.
  • the aforementioned dispersing agents as well as lignosulfonates can be included.
  • the required amount of the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or- diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent.
  • concentration in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active toxicant per acre.
  • the pesticides contemplated herein prevent attack by insects, mites and nematodes upon plants or other material to which the pesticides are applied, and they have relatively high residual toxicity. With respect to plants, they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolyais as would materially decrease the desirable pesticidal characteristic of the toxicants or impart undesirable characteristic for instance, phytotoxicity, to the toxicants.
  • the toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants. They may also be used in combination with other pesticidally active compounds. When used as miticides they will normally be applied to the foliage of the plants to be treated. It will be appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Luminescent Compositions (AREA)

Abstract

Novel phosphorous. esters of cyanohydrins which exhibit outstanding pesticidal activity. A method of controlling pests by subjecting the pests to a pesticidally active amount of a compound of this invention is also covered.
The esters have the general formula:
Figure imga0001
wherein X is 0 or S;
  • R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C15), whereby C3-C15 can be branched or unbranched, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or more halo; cycloalkyl (C3-C8), alkenyl, phenyl, benzyl, pyridinyl, pyrimidinyl, furanyl, pyranyl, naphthalene, thiophene. all of which may be optionally substituted with one or more halogen, nitro, cyano, allyloxy, trihalomethyl, alkyl, alkylthio, alkoxy, or aryloxy, aryloxy alkyl, which can be further substituted with alkoxy, halogen, alkyl, or trihalomethyl groups; taken together R and R, may form a 5 or 6 membered carbocyclic ring.
  • R2 and R3 can be the same or different and are independently:
    • a) alkyl (C1-C10),
    • b) alkylthio (C,-Ca),
    • c) haloalkyl (C1-C8),
    • d) alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time,
    • e) alkyl or dialkyl amino (CI-Ca).
    • f) phenyl or benzyl which can be optionally substituted with one or more nitro, cyano, halogen, trihalomethyl, alkyl, alkoxy, alkylthio or aryloxy,
    • g) thioaromatic radicals, and
    • h) oxyaromatic radicals.

Description

  • This invention relates to novel phosphorous esters of cyanohydrins and methods of preparing same. This invention is also directed to a pesticidal composition comprising an acceptable carrier and a pesticidally effective amount of a compound of this invention, as well as to a method of controlling pests which comprises subjecting the pests to a pesticidally effective amount of a compound of this invention.
  • Certain phosphate esters of cyanohydrins are disclosed in U.S. Patent 2,965,533, which issued on December 20, 1960 and which is assigned to Shell Oil Company. The phosphates disclosed in this patent are based on the diethyl chlorophosphate moiety:
    Figure imgb0001
  • As an example, the patentee reacts acetone cyanohydrin with A to yield Diethyl 1-cyano-1-methyl ethyl phosphate as shown below.
    Figure imgb0002
  • According to the present invention one of the 0-ethyl groups is replaced by an S-n-propyl group which unexpectedly increases the broad cpectrum pesticidal activity over the compounds disclosed in U.S. Patent 2,965,533.
  • The novel compounds can be represented by the following generic formula:
    Figure imgb0003
    wherein X is 0 or S;
    • R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C15). whereby C3-C15 can be branched or unbranched, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or more halo; cycloalkyl (C3-C8), alkenyl, phenyl, benzyl, pyridinyl, pyrimidinyl, furanyl, pyranyl, naphthalene, thiophene, all of which may be optionally substituted with one or more halogen, nitro, cyano, allyloxy trihalomethyl, alkyl, alkylthio, alkoxy, or aryloxy, aryloxy alkyl, which can be further substituted with alkoxy, halogen, alkyl, or trihalomethyl groups; taken together R and R1 may form a 5 or 6 membered carbocyclic ring.
    • R2 and R3 can be the same or different and are independently:
      • a) alkyl (C1-C10),
      • b) alkylthio (C1-C8),
      • c) haloalkyl (C1-C8),
      • d) alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time,
      • e) alkyl or dialkyl amino (C1-C8),
      • f) phenyl or benzyl which can be optionally substituted with one or more nitro, cyano, halogen, trihalomethyl, alkyl, alkoxy, alkylthio or aryloxy,
      • g) thioaromatic radicals, and
      • h) oxyaromatic radicals.
  • Compositions falling within the above generic formula exhibit biological activity as pesticides to a greater or lesser extent. Some exhibit very powerful activity in extremely small dosages while others require larger dosages to be effective.
  • . In general, the compounds which are preferred for pesticidal activity are those of the above generic formula wherein:
    • X is 0;
    • R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C6). phenyl substituted with aryloxy, further substituted with halogen:
    • R2 and R3 can be the same or different and are independently alkylthio and alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time.
  • Compounds which are most preferred are represented by namenclature and structure as follows:
    Figure imgb0004
    Figure imgb0005
  • In general, the phosphorous esters of this invention can be conveniently prepared utilizing appropriate aldehydes and ketones as starting materials. These are converted to their corresponding cyanohydrins (1-4) and then reacted with a phosphorylating group as shown below.
    Figure imgb0006
    wherein the values of X, R, R1, R2 and R3 are as indicated previously.
  • According to the above scheme, the aldehyde or ketone (C) can be converted to cyanohydrin (D) using one of the four methods listed or variations thereof. The choice of which method is used is dependent upon the substituents R and R1.
  • Conversion of G→ D using methods 1.2, and 3 are detailed in Examples I, 11 and III.
  • Conversion of D→ E occurs by reacting one equivalent of cyanohydrin with an appropriate chloro phosphorous compound in the presence of at least one equivalent of an acid acceptor, preferably in an inert solvent.
  • The acid acceptor utilized in this reaction scheme (D→ E) can be either an organic or inorganic base. Illustrative of organic bases that are useful acid acceptors are tertiary amines, such as triethylamine, 4-N,N-dimethylamino pyridine, pyridine, trimethyl amine, collidine or 1,4-diazobicyclo [2.2.2] octane; bases such as sodium carbonate and potassium carbonate are illustrative of inorganic bases that are useful acid acceptors.
  • In general, any organic solvent that is inert to the reactants or reaction conditions may be employed in the reaction scheme shown above. Illustrative of organic solvents which are generally suitable for use in conducting these reactions are saturated, unsaturated and aromatic hydrocarbons, e.g. hexane, cyclohexane, octane, cyclohexene, dodecane, naptha, decalin, kerosene, cyclopentane, benzene, toluene, xylene, napthlene or the like; others such as dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethyoxybenzen, the dialkyl ethers of ethylene glycol, or propylene glycol or chlorinated aliphatic hydrocarbons, as for example, chloroform, dichloromethane 1,1-dichloroethane, carbon tetrachloride, and the like, are also acceptable.
  • The reaction sequence D→E may also be conducted in a solvent which functions as an acid acceptor. Illustrative of such multifunctional colvcnts are N,N-dimethylaniline, pyridine, collodine or any like aromatic or heterocyclic tertiary amine compound.
  • The reaction sequence (C→ D→ E) can be conducted over a broad temperature and pressure range to yield the desired products, preferably, these reactions are conducted at a temperature of -40°C to about 60°C and at atmospheric or autogeneous pressure.
  • The phosphorous halides utilized as reactants in the scheme D→ E generally are known materials which can be obtained from commercial sources or prepared in accordance with conventional methods known to those skilled in the art.
  • The following pesticidally active compounds are illustrative of compounds within the purview of the above generic formula and which can be conveniently prepared by the process of this invention simply by selecting appropriate reactants for use in the procedures described below.
    • O-(1-eyanoethyl)-O-ethyl-S-n-propylthiophosphane.
    • O-(2,2,2-trichloro-1-cyanoethyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(2-methyl-l-eyanopropyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(2,2-dimethyl-1-cyanopropyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(2-cyano-2-propyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(1,1,1-trichloro-2-cyano-2-propyl)O-ethyl-S-n- propylthiophosphate.
    • O-(1,1,1-trichloro-2-cyano-2-propyl)-O-ethyl-N-isopropyl phosphoroamidate.
    • O-(1,1,1-trichloro-2-cyano-2-propyl)-O-ethylphenyl thionophosphonate.
    • O-(1,1,1-trifluoro-2-cyano-2-propyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(1,1,1,3,3,3-hexachloro-2-cyano-2-propyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(1,1,3-triohloro-1,3,3-trifluoro-2-cyano-2-propyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(2-cyano-2-butyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(l-cyano-l-cyclopropyl ethyl)-0-ethyl-S-n-propylthio- phosphate.
    • O-(5-chloro-2-cyano-2-pentyl)-O-ethyl-S-n-propyithio- phosphate.
    • O-(1-cyanohexyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(1-cyanooctyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(3-methoxy-1-cyanobutyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(1-cyanocyclobexyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(1-cyanocyclohexyl)-0-ethyl-S-n-propylphosphorodi-thioate.
    • O-(α -cyanobenzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α -cyanobenzyl)-0-ethyl-S-n-butylthiophosphate.
    • O-(α -cyanobenzyl)-O-ethyl-S-n-propylphosphorodithioate
    • O-(α -cyano-2-chlorobenzyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(α-cyano-2-allyloxybenzyl)-O-cthyl-S-n-propyl- thiophosphate.
    • O-(α -cyano-2-methylbenzyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(α -cyano-2-nitrobenzyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(α -cyano-3-fluorobenzyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(α -cyano-3-trifluoromethylbenzyl-O-ethyl-S-n-propylthiophosphate.
    • O-(α-cyano-4-chlorobenzyl)-4-ethyl-S-n-propylthio- phosphate.
    • O-(α -cyano-2,4-dichlorobenzyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(α -cyano-2,6-dichlorobenzyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(α -cyano-3-nitro-2,6-dichlorobenzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α -cyano-2,3,4,5,6-penfluoroberzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(2,4-dichloro-α-cyano-α-methylbenzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(2-bromo-l-cyano-3-phenyl-2-propenyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α-eyano-2-pyridylmethyl)-O-ethyl-S-n-propylthio- phosphate.
    • O-(α-cyano-6-methyl-2-pyridylmethyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α-cyano-1-(2-pyridylethyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(α-cyano-3-phenoxybenzyl)-O-ethyl-S-n-propyl- thiophosphate.
    • O-(α-cyrno-3-phenoxybenzyl)-O-ethyl-S-isopropylthio- phosphate.
    • O-(α-cyano-3-phenoxybenzyl)-O-ethyl-S-n-propylphos- phordithioate.
    • O-(α-cyano-3-phenoxybenzyl)-O-ethyl-ethyl-thionophosphonate.
    • O-(α-cyano-3-(4'-chiorophenoxybenyl)-O-ethyl-S-n-propylthiophosphate.
    • O-[α-cyano-6-(2,4-dichlorophenoxy)-2-pyridine methyl]-O-ethyl-S-n-propylthiophosphate.
    • O-(8-eysno-8-pEneadeeyl)-O-cthyl-S-n-propylthiophosphate.
    • O-(5-cyano-5-tridccyl)-O-ethyl-S-h-propylthiophosphate.
    • O-(3-cyano-3-dodecyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(5-ethoxy-3-cyano-3-pentyl)-0-ethyl-S-n-propyl- thiophosphate.
    • O-(α-cyano-3-methylcyclohexyl)-O-ehbyl-S-n-propyl- thiophosphate.
    • O-(α-cyano-2,4,6-trimethoxybenzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α-cyano-3-(4'-tertbutylphenoxybenzyl)-O-ethyl-S-n-propylthiophosphate.
    • O-(α-cyano-4-phenoxybenzyl)-O-ethyl-S-n-propyl-thiophosphate.
    • O-(α-cyano-4-phenylbenzyl)-O-ethyl-S-n-propylthio- phosphate.
  • The following examples will illustrate the present invention.
    • Example 1 Preparation of O-(α-cyanobenzyl)-O-ethyl-S-n-propvlthiophosphate.
  • A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel and drying tube. The glassware was dried and to this was charged 21.2 grams (0.2 mole) benzaldehyde and 19.5 grams (0.3 mole) potassium cyanide dissolved in 70 ml of water. The reaction flask was cooled to 10-15°C using a water/ice bath. To this was added 70 ml of 40% sulfuric acid over a 60 minute period. After the addition was complete, the reaction was allowed to warm to room temperature and stir for an additional two hours.
  • At the end of this time the reaction mixture was extracted with carbon tetrachloride (3x75 ml), washed the combined carbon tetrachloride layers with water (2x50 ml), dried the carbon tetrachloride layer with anhydrous magnesium sulfate, filtered and concentrated to yield benzaldehyde cyanohydrin.
  • To a 100 ml two-neck round bottom flask equipped with thermometer, water condenser and drying tube, magnetic stirring bar and heating mantel, was charged 5.0g (0.0376 mole) benzaldehyde cyanohydrin, 3.4g (0.043 mole) pyridine and 40 ml acetonitrile. The contents were then stirred for two hours at room temperature at which time 7.6g (0.0376 mole) of 0-ethyl-S-n-propyl phosphorochloridate was added. The mixture was then stirred overnight at room temperature.
  • The following day a TLC taken of the crude reaction mixture showed that the reaction had not gone to completion. 3.4g of (0.043 mole) of pyridine was edded to the flask and the reaction mixture heated to 40°C for four hours at which time the acetonitrile was removed under vacuum and the residue taken up.in 400 ml of ethyl ether and washed with water (2x100 ml). The ether layer is then dried with anhydrous magnesium sulfate, filtered and concentrated under vacuum. The resulting residue is then purified by means of a low pressure liquid chromatography colum to yield 2.4 gram of the desired product as an oil. (n23 D 1.5118)
  • Calcd for C13H18NO3PS: C,52.16; H,6.06 Found: C,52.26; H,6.05
    • Example 2 Preparation of O-(α-cyano-2,3,4,5,6-pentafluoru- benzyl)-0-ethyl-S-n-propylthiophosphate.
  • A 100 ml round bottom flask fitted with thermometer, water condenser with drying tube and magnetic stirring bar has charged into it 2.8g (.033 mole) acetone cyanohydrin, 3 drops triethylamine and 50 ml carbon tetrachloride. The reaction mixture is cooled to 0°C using a water/ice bath. 5.9g (.03 mole) of pentafluoro benzaldehyde is added to the reaction mixture at a rate which allows the temperature to be maintained between 5-15°C. After all the aldehyde is added the reaction is brought up to room temperature and stirred overnight.
  • The reaction is cooled to 15°C (water/ice bath) and 2.4g (.03 mole) pyridine is added followed by the addition of 6.0g (.03 mole) 0-ethyl-S-n-propyl phosphoro chloridate while maintaining a temperature of less than 20°C. After the chloride is added the reaction is brought to room temperature and stirred overnight.
  • Additional carbon tetrachloride is added to the reaction mixture and then the mixture is washed several times with water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue is then purified by means of a low pressure liquid chromatography column to yield 1.0 gram of the desired product as an oil (n21 D 1.4720).
  • Calcd for C13H13F5NO3PS: C,40.11; H,3.37 Found: C,40.63; H,3.15
    • Example 3 Preparation of O-(α-cyano-4-isopropylbenzyl)-O-ethyl-S-n-propylthiophosphate.
  • A 100 ml round bottom flask fitted with thermometer, water condenser with drying tube and magnetic stirring bar has charged into it 6.0g (.0405 mole). 4-isopropylbenzaldehyde, 4:8g (.0486 mole) trimethylsilyl cyanide, 50 ml methylene chloride and a catalytic amount of triphenyl phosphine and zinc chloride. The material was stirred overnight at room temperature and then transferred to a 250 ml flask at which time 60 ml of 3N hydrochloric acid was added end the mixture stirred for three hours at room temperature. The material was taken up in ethyl ether, dried over anhydrous magnesium sulfate, filtered and concentrated in vecunm.
  • To 7.2g (.041 mole) of the above concentrate dissolved. in 50 ml of ethyl ether was added 8.3g (.041 mole) O-ethyl-S-n-propyl phosphorochloridate at 10°C. To this mixture was added 3.6g (.045 mole) pyridine while maintaining temperature below 20°C. After the addition of pyridine was complete the reaction was allowed to warm to room temperature and stir over the weekend.
  • Work-up consisted of filtering off solid (amine salt), washing the ether layer with water, drying the ether layer with anhydrous magnesium sulfate, filtering and concentrating in vacuum. The resulting residue is purified by means of a low pressure liquid chromatography column to yield 1.7 grams of the desired product as an oil (n23 D 1.5055).
  • Calcd for C16H24NO3PS: C,59.81; H,7.49 Found: C,59.58; H,7.44
  • Examples 4-45 illustrate other compounds of the present invention which were prepared by methods detailed in this invention.
  • Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
  • Selected apenies of the now compounds were evaluated to determine their perticidal ectivity against mites, nematodes, and certain inaccta, including en aphid, a caterpillar. & beetle and a fly.
  • Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 150 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thus-prepared stock suspension contained 0.5 percent by weight of compound. The concentrations in parts per million by weight employed in the tests described below were obtained by appropriate dilutions of the stock suspension with water.
  • The test procedures were as follows:
    • Adults and nymphal stages of the bean aphid (Aphis fabae Scop.) reared on potted dwarf nasturtium plants at 65-70°F. and 50 + 5 percent relative humidity, constituted the test insects. For testing purposes, the number of aphids per pot was standardized to 100-150 by trimming plants containing excess aphids.
  • The test compounds were formulated by diluting the stock suspension with water to give c suspension containing 500 parts of test compound per million parts of final formulation.
  • The potted plants (one pot per comperund Leated) infested with 100-150 aphide, were placed on a revolving turntable and aprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 acconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting. Temperature and humidity in the test room during the 24 hour holding period were 65-70°F, and 50 ± 5 percent, respectively. Aphids which fell onto the paper and were unable to remain standing after being uprighted were considered dead. Aphids remaining on the plants were observed closely for movement and those which were unable to move the length of the body upon stimulation by prodding were considered dead.
  • Third instar larvae of the southern armyworm (Spodoptera cridania, (Cram.)). reared on Tendergreen bean plants at a temperature of 80 ± 5°F, and a relative humidity of 50 ± 5 percent, constituted the test insects.
  • The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and aprayed with 100-110 milliliters of test compound formulation by use of a DeVilbias spray gun set ct 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on plants. When dry, the paired leaves were separated and each one was placed in a 9 centimeter Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80-85°F. for three days. Although the larvae could easily consume the whole leaf within twenty-four hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation by prodding, were considered dead.
  • Third instar larvae of the Mexican bean beetle (Epilachna varivestis, Muls.), reared on Tendergreen bean plants at a temperature of 80 + 5°F. and 50 + 5 percent relative humidity, were the test insects.
  • The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no teet compound were also aprayed on plants. When dry, the paired leaves were separated nnd each was placed in a 9 cantimetor Petri dich lined with moistened filter paper. Five randomly selected larvae were introduced into each dich, and the dishes were closed. The closed dishes were labeled and held at a temperature of 80 + 5 F. for three days. Although the larvae could easily consume the leaf within 24 to 48 hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation, were considered dead.
  • Four to six day old adult house flies (Musca domestica, L.), reared according to the specifications of the Chemical Specialties Manufacturing Acsociation (Blue Book, McNair-Dorland Co.. N. Y. 1954; pages 243-244, 261) under controlled conditions of 80 + 5°F. and 50 ± 5 percent relative humidity, were the test insects. The flies were immobilized by anesthetizing with carbon dioxide and twenty five immobilized individuals. males and females, were transferred to a cage consisting of a standard food strainer about five inches in diameter which was inverted over a wrapping-paper-covered surface. The test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final formulation, by weight. Ten milliliters of the test formulation were added to a soufflè cup containing a one-inch square of an absorbent cotton pad. This bait cup was introduced and centered on the blotting paper under the food strainer prior to admitting the anesthetized flies. The caged flies were allowed to feed on the bait for twenty four hours, at a temperature of 80 ± 5°F, and the relative humidity of 50 ± 5 percent. Flies which showed no sign of movement on prodding were considered dead.
  • Adults and nymphal stages of the two-spotted mite (Tetranychus urticae Koch), reared on Tendergreen bean plants at 80 ± 5°F and 50 ± 5 percent relative humidity were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. 150-200 Mites, a sufficient number for testing, transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and'sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 seconds, was sufficient to wet the plants to nun-off. As a control, 100-110 milliliters of water solution containing acetone and emulsifier in the same concentration as the test compound formulation, but containing no test compound, were also sprayed on infested plants. The sprayed plants were held at 80 + 5°F and 50 ± 5 percent relative humidity for six days, after which a mortality count of motile forms was made. Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living.
  • Infective migratory larvae of the root-knot nematode, Meloidogyne incognita ver. acrita, reared in the greenhouse on roots of tomato (Florida M-1) and cucumber (National pickling), constituted the test organism. This particular nematode incites distinct galls or knots on the roots of certain plants. Infected roots, containing egg masses, were removed from the stock culture and cleaned of soil by shaking and washing with tap water. Roots were finely chopped, then vigorously shaken in a 0.5 percent NaOCl solution for 4 minutes. To separate the nematode eggs from root tissue, the mixture was poured through a 32-mesh sieve nestled in a 500-mesh sieve followed by a gentle stream of water to remove any trace of NaOl.
  • The trapped eggs were rinsed with water into a 50-mt beaker. Samples of the egg suspension were counted with the aid of a stereoscopic microscope. 4000 to 6000 eggs were added to a series of pint mason jars, each containing 180 cc. of soil. The jars were capped and mixed thoroughly to insure uniform infestation of the soil. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 3.3 mg of test compound per 10 mℓ of final formulation which when added to the jar of coil was approximately equal to a rate of 28 kilogram of test compound per acre. Following addition of formulation, the jars were tightly capped, and the contents were thoroughly mixed on a ball mill for five minutes. The jars remained capped for 48 hours after which the contents were transferred to three inch diameter pots. The coil was then planted with cucumber seeds, and since cucumber is susceptible to root-knot nematode attack, it served as an indicator crop. The pots were then placed in a greenhouse. After 4-6 weeks, the cucumber plants were removed from the pots, the roots were washed free of adhering soil, and directly compared with the roots of similar plants grown in infested but untreated soil. The averaged degree of gall formation on the roots of the cucumber plants was the basis for ascertaining nematode control.
  • The results of these tests.are set forth in Table 11 below. In these tests the pesticidal activity of the compounds at the indicated dosage rate against aphid, mite, Southern Armyworm, Bean Beetle house fly and root-knot nematode was rated as follows:
    • A = excellent control
    • B - partial control.
    • C = no control
  • Dashes indicate no test conducted.
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
  • It will be understood that the pest species employed in the above tests arc merely representative of a wide variety of plant pests that can be controlled by the use of the compounds of this invention. The compounds contemplated in this invention may be applied as mite ovicides and miticides according to methods known to those skilled in the art. Moreover it has been found that the compounds of the instant invention are useful as fumigants for grain insects, have soil insecticidal activity against the corn root worm, and also possess systemic activity. Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
  • Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying and dispersing agents.
  • The choice of dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re- emulsify the toxicant after it is applied to the plant and wash it off the plant. Nonionic, anionic. amphoteric or cationic dispersing and emulsifying agents may be employed; for example, the condensation products of alkylene oxidec with phenol and organic acids,. alkyl aryl sulfonates, complex, other alcohols, quaternary ammonium compounds, and the like.
  • In the preparation of wettable powder or dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included.
  • The required amount of the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or- diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active toxicant per acre.
  • The pesticides contemplated herein prevent attack by insects, mites and nematodes upon plants or other material to which the pesticides are applied, and they have relatively high residual toxicity. With respect to plants, they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least auch decomposition, oxidation, and hydrolyais as would materially decrease the desirable pesticidal characteristic of the toxicants or impart undesirable characteristic for instance, phytotoxicity, to the toxicants. The toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants. They may also be used in combination with other pesticidally active compounds. When used as miticides they will normally be applied to the foliage of the plants to be treated. It will be appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

Claims (11)

1. A phosphorous ester of a cyanohydrin of the general formula:
Figure imgb0029
wherein X is 0 or S;
R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C15), whereby C3-C15 can be branched or unbranched, and wherein the alkyl chain can be substituted or unsubstituted with alkylthio, alkoxy, or one or more halo; cycloalkyl (C3-C8), alkenyl, phenyl, benzyl, pyridinyl, pyrimidinyl, furanyl, pyranyl, naphthalene, thiophene, all of which may be optionally substituted with one or more halogen, nitro, cyano, allyloxy trihalomethyl, alkyl, alkylthio, alkoxy, or aryloxy, aryloxy alkyl, which can be further substituted with alkoxy, halogen, alkyl, or trihalomethyl groups; taken together R and R1 may form a 5 or 6 membered carbocyclic ring.
R2 and R3 can be the same or different and are independently:
a) alkyl (C1-C10).
b) alkylthio (C1-C8),
c) haloalkyl (C1-C8),
d) alkoxy (C1-C8) with the proviso that
R2 and R3 may not be alkoxy at the same time,
e) alkyl or dialkyl amino (C1-C8),
f) phenyl or benzyl which can be optionally substituted with one or more nitro, cyano, halogen, trihalomethyl, alkyl, alkoxy, alkylthio or aryloxy,
g) thioaromatic radicals, and
h) oxyaromatic radicals.
2. An ester as claimed in claim 1 wherein X is O.
3. An ester as claimed in claim 2 wherein R and R1 are the same or different and are independently hydrogen, lower alkyl (C1-C6), phenyl substituted with aryloxy, further substituted with halogen.
4. An ester as claimed in claim 3 wherein R2 and R3 can be the same or different and are independently alkylthio and alkoxy (C1-C8) with the proviso that R2 and R3 may not be alkoxy at the same time.
5. 0-(α-Cyanobenzyl)-0-ethyl-S-n-propylthiophosphate.
6. 0-(2-Cyano-2-propyl)-0-ethyl-S-n-propylthiophosphate.
7. 0-(2-Methyl-l-cyanopropyl)-0-ethyl-S-propylthiophosphate.
8. 0-(α-Cyano-3-[2',4'-dichlorophenoxy- benzyl)-0-cthyl-S-n-propylthiophosphate.
9. O-(1-Cyanoethyl)-O-ethyl-S-propylthio- phosphate.
10. A pesticidal composition comprising an acceptable carrier and as the active toxicant a pesticidally effective amount of an ester as claimed in any one of the preceding claims.
11. A method of controlling nematodes, insects and mites which comprises subjecting them to a nematocidally, insecticidally or miticidally effective amount of an ester as claimed in any one of claims 1 to 9.
EP81303181A 1980-07-16 1981-07-10 Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same Expired EP0044214B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81303181T ATE15373T1 (en) 1980-07-16 1981-07-10 PHOSPHORIC ESTERS OF CYANHYDRIN, PESTICIDE PREPARATIONS CONTAINING THEM AND THEIR USE AS PESTICIDES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16928480A 1980-07-16 1980-07-16
US169284 1993-12-20

Publications (3)

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EP0044214A2 true EP0044214A2 (en) 1982-01-20
EP0044214A3 EP0044214A3 (en) 1982-04-28
EP0044214B1 EP0044214B1 (en) 1985-09-04

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EP81303181A Expired EP0044214B1 (en) 1980-07-16 1981-07-10 Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same

Country Status (16)

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EP (1) EP0044214B1 (en)
JP (1) JPS5748992A (en)
AT (1) ATE15373T1 (en)
AU (1) AU545084B2 (en)
BR (1) BR8104533A (en)
DE (1) DE3172135D1 (en)
DK (1) DK315881A (en)
ES (1) ES503974A0 (en)
GR (1) GR75726B (en)
IL (1) IL63276A (en)
IN (1) IN154876B (en)
NZ (1) NZ197634A (en)
PH (1) PH19932A (en)
PT (1) PT73373B (en)
SU (2) SU1118275A3 (en)
ZA (1) ZA814676B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0058864A1 (en) * 1981-02-21 1982-09-01 Bayer Ag Process for preparing phosphoric acid cyanohydrin esters, phosphoric acid cyanohydrin esters, pesticides containing them and their use
US4454019A (en) * 1981-01-28 1984-06-12 Toa Nenryo Kogyo Kabushiki Kaisha Process for producing optically anisotropic carbonaceous pitch
EP0213393A1 (en) * 1985-08-07 1987-03-11 Bayer Ag Phosphonic-acid esters

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09239372A (en) * 1996-03-08 1997-09-16 Meisei Ri Treatment of aqueous fluid and device therefor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2494284A (en) * 1949-01-12 1950-01-10 American Cyanamid Co Cyanoalkyl phosphates and method of preparation
DE1047776B (en) * 1958-03-28 1958-12-31 Bayer Ag Process for the preparation of thionophosphoric acid esters
US2965533A (en) * 1956-04-26 1960-12-20 Shell Oil Co Phosphate esters of cyanohydrins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2494284A (en) * 1949-01-12 1950-01-10 American Cyanamid Co Cyanoalkyl phosphates and method of preparation
US2965533A (en) * 1956-04-26 1960-12-20 Shell Oil Co Phosphate esters of cyanohydrins
DE1047776B (en) * 1958-03-28 1958-12-31 Bayer Ag Process for the preparation of thionophosphoric acid esters

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACT, Vol. 69, No. 17, 21st October 1968, page 6310, No. 67489j Columbus, Ohio, U.S.A. A.N. PUDOVIK et al.: "Reaction of Phosphonic and Phosphinic Acid Esters with the Nitriles of alfa-Keto Carboxylic Acids" & Khim. Org. Soedin. Fosfora, Akad. Nauk SSSR, Old. Obshch. Tekh. Khim. 1967, 42-52 *
Derwent Japanese Patents, Section Chemical, Derwent Publications Ltd., Week 14 19-03-1968 Vol. 7, No. 11, Section 5, page 8; & JP-B-43 007 358, (Nippon Noyaku K.K.) 19-03-1968 *
Journal of General Chemistry of the USSR, Vol. 45, No. 11, Part 1, 20th April 1976, pages 2369-2371 V.E. SHISHKIN et al.: "Alkyl and Aryl Cyanoalkyl Methylphosphonates" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4454019A (en) * 1981-01-28 1984-06-12 Toa Nenryo Kogyo Kabushiki Kaisha Process for producing optically anisotropic carbonaceous pitch
EP0058864A1 (en) * 1981-02-21 1982-09-01 Bayer Ag Process for preparing phosphoric acid cyanohydrin esters, phosphoric acid cyanohydrin esters, pesticides containing them and their use
US4567168A (en) * 1981-02-21 1986-01-28 Bayer Aktiengesellschaft Cyanohydrin phosphonates as pesticides
EP0213393A1 (en) * 1985-08-07 1987-03-11 Bayer Ag Phosphonic-acid esters
US4757058A (en) * 1985-08-07 1988-07-12 Bayer Aktiengesellschaft Phosphonic acid ester pesticides

Also Published As

Publication number Publication date
IL63276A0 (en) 1981-10-30
DK315881A (en) 1982-01-17
PT73373B (en) 1982-08-09
AU7274181A (en) 1982-01-21
ZA814676B (en) 1982-07-28
IL63276A (en) 1985-09-29
AU545084B2 (en) 1985-06-27
PT73373A (en) 1981-08-01
DE3172135D1 (en) 1985-10-10
EP0044214B1 (en) 1985-09-04
BR8104533A (en) 1982-03-30
SU1134563A1 (en) 1985-01-15
GR75726B (en) 1984-08-02
ATE15373T1 (en) 1985-09-15
EP0044214A3 (en) 1982-04-28
JPS6348279B2 (en) 1988-09-28
ES8302725A1 (en) 1983-02-01
IN154876B (en) 1984-12-22
ES503974A0 (en) 1983-02-01
PH19932A (en) 1986-08-14
NZ197634A (en) 1985-07-12
JPS5748992A (en) 1982-03-20
SU1118275A3 (en) 1984-10-07

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